2,4-DICHLOROPHENOLSAFE HANDLING GUIDE

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ContentsIntroduction..................................................... 1Personnel Training .......................................... 1Physical Properties .......................................... 1Chemistry and End Uses ................................. 2Hazards ............................................................ 2Handling Precautions ...................................... 3Protective Measures and Equipment .............. 3First Aid ........................................................... 4Shipping Information ...................................... 5Sampling, Unloading, and Spill Clean-Up ..... 6Storage ............................................................. 8Commitment to Responsible Care®

and Product Stewardship ......................... 8Important Notes............................................... 9

Introduction2,4-Dichlorophenol (DCP) is an important inter-mediate in the manufacture of 2,4-dichloro-phenoxyacetic acid (2,4-D), the well-knownindustrial commodity herbicide. It is also usedin the manufacture of other pesticide productsand pharmaceuticals.

As an acknowledged leader in the productionof DCP, Dow AgroSciences is firmly committedto advancing and maintaining the highest stan-dards of purity, quality, and safety. Because DCPcan pose significant health hazards, safe-handling procedures must be observed, and allpersonnel working with this product must bewell trained. For new customer sites, DowAgroSciences requires and provides a site stew-ardship assessment prior to the first shipmentof product.

2,4-DichlorophenolSafe Handling Guide

Personnel TrainingPersonnel handling 2,4-dichlorophenol mustunderstand its hazards, must be trained to avoidthose hazards, and must be given specific in-structions concerning the personal protectiveequipment required for particular situations.Safety equipment must be readily available andproperly maintained. Workers must be trainedin procedures to follow if exposure occurs.

The emphasis should be on preventing expo-sure, not reacting to an exposure. Safety proce-dures and material safety data sheets (MSDS)must be reviewed with workers according toOSHA Hazard Communication Standard 29 CFR1910.1200. The entire training program must bedocumented in writing, and records must bekept of individual participation.

Physical PropertiesDCP is a white, crystalline solid at room tem-perature. When molten, it is a colorless liquid.It has a strong phenolic odor, which serves as agood indicator of its presence.

DCP Physical PropertiesFreezing Point 108°F/42°CBoiling Point 419°F/215°CVapor Pressure @ 20°C 0.10 mm HgVapor Density (Air = 1) 5.6Water Solubility 0.45 g/100 gSpecific Gravity (60°C/4°C) 1.382Molecular Weight 163Flash Point (TCC) 219°F/104°C

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Chemistry and End UsesDCP exhibits two major types of reactivity: re-actions of the phenolic –OH group and electro-philic substitution in the aromatic ring. Themost important type of reactivity is related to theacidity of the –OH group. DCP reacts with basesto form salts. For example, reaction with sodiumhydroxide yields the sodium salt of DCP.

The sodium salt of DCP can then react furtherwith alkyl halides or sulfates to form 2,4-dichlorophenyl ethers. For example, reactionwith methyl iodide yields 2,4-dichloroanisole.

The sodium salt of DCP also reacts readilywith acid chlorides or acid anhydrides to pro-duce esters. For example, reaction with benzoylchloride yields 2,4-dichlorophenyl benzoate.

An example of electrophilic ring substitutionin 2,4-dichlorophenol is the reaction with chlo-rine, which yields 2,4,6-trichlorophenol.

End UsesDCP and its alkali salts are used in the manu-facture of a wide variety of chemical products.A common end use for DCP is in the productionof phenoxy herbicides. For instance, the sodiumsalt of DCP is reacted with sodium chloroacetateto produce 2,4-dichlorophenoxyacetic acid,commonly known as 2,4-D. Additional applica-tions for chemicals derived from DCP includepharmaceuticals, fungicides, and insecticides.

HazardsIn the interest of environmental and personalsafety and in compliance with hazard commu-nication policies, Dow AgroSciences supplies anMSDS for DCP. All personnel should read thisinformation carefully and understand the poten-tial hazards associated with DCP before han-dling it. In addition, all applicable federal, state,and local health and safety laws and regulationsshould be followed.

MSDSTo display or print a copy of the dichlorophenolMSDS from the Dow AgroSciences web site,visit www.dowagro.com, click on the “U.S. La-bel and MSDS System” link on the home page,and follow the on-screen instructions.

To obtain copies of the MSDS by fax, pleasecall the Dow AgroSciences self-service docu-ment center.

1-800-891-9157If you are in California, call 1-888-847-6858 forthe document center.

Copies of the MSDS can also be ordered bytelephone from Dow AgroSciences CustomerService.

1-317-337-7850

Stability and ReactivityDCP is stable under normal handling and stor-age conditions. However, the product can de-compose at elevated temperatures. Hydrochloricacid and other toxic, irritating products can beproduced if DCP is burned.

CorrosivityDCP is moderately corrosive. The suggestedmaterial of construction for handling solid andliquid DCP is carbon steel. Copper is corrodedby DCP at elevated temperatures and is there-fore not recommended for use. Moisture in DCPincreases the potential for corrosion, thereforerendering carbon steel inadequate as a materialof construction. If the DCP contains moisture,materials such as Hastelloy C or Monel, whichcontain a greater nickel content, should be used.Stainless steel should be avoided due to the po-tential for stress-corrosion cracking.

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Physical HazardsEye: Direct contact can cause severe irritationwith corneal injury, which could result in per-manent impairment of vision, even blindness.Handling DCP at elevated temperatures can gen-erate vapor levels sufficient to cause eye irrita-tion. Contact with heated material can also causethermal burns.

Skin: DCP is more readily absorbed through theskin when in solution and especially whenmolten. Molten or hot DCP is immediately ab-sorbed through the skin in amounts that havecaused death to humans. Rapid death in humanshas been caused by skin exposure without im-mediate decontamination. Amounts of moltenDCP that cover as little as 1% body surface area(e.g., palm-of-hand-sized) could result in death.

Ingestion: Small amounts of DCP that might beswallowed incidental to normal handling opera-tions are unlikely to cause injury. However, swal-lowing large amounts could cause injury.Ingestion can also cause chemical burns of themouth and throat.

Inhalation: Although the formation of DCP dustis unlikely, such dust can result in severe irrita-tion in the upper respiratory tract (nose andthroat). Elevated temperatures can generate va-por levels sufficient to cause respiratory irrita-tion.

Handling PrecautionsBecause of the hazards associated with DCP,constant care must be exercised, and adequateprotective measures and equipment fully uti-lized to avoid harmful effects to personnel or theenvironment. Written procedures for handlingDCP in all applicable operations should also beestablished. A self-contained system with dry-break connections and sufficient ventilation isrecommended in areas where potential exposurecan occur. Use extreme caution when handlinghot or molten DCP. Molten or hot DCP is imme-diately absorbed through the skin in amounts thathave caused death to humans. Rapid death in hu-mans has been caused by skin exposure withoutimmediate decontamination. Amounts of moltenDCP that cover as little as 1% body surface area(e.g., palm-of-hand-sized) could result in death.

Protective Measuresand EquipmentSee First Aid section on page 4 for decontamina-tion guidelines.

The sharp, pungent odor and low odor thresh-old of DCP provide good early warning proper-ties of the presence of DCP. Adequate ventilationshould be provided to control airborne concen-trations below exposure guidelines when han-dling DCP.

Exposure LimitsDow AgroSciences’ Industrial Hygiene Guide-line (IHG) for DCP is 1 ppm. The IHG is basedupon an 8-hour time-weighted average exposureby vapor inhalation. It should also be noted thatinhalation might not be the only route of expo-sure. Skin contact is another potential exposureroute, and molten or hot DCP can be immedi-ately absorbed through the skin in amounts thathave caused rapid death in humans. Absorptionthrough skin accelerates with temperature suchthat additional measures to minimize exposureto hot or molten DCP should be considered.

Respiratory ProtectionWhen DCP levels are below the exposure guide-line, personnel in areas where the material isstored or used should not need to use respira-tory protection. However, if personnel are han-dling DCP at elevated temperatures (whenvapors are likely to be generated) without suffi-cient ventilation, or if respiratory irritation is ex-perienced, use of a NIOSH-approved, full-face,air-purifying respirator for organic vapors is rec-ommended. Suitable positive-pressure, self-con-tained breathing apparatus should be used forlonger-term exposure in emergency situations,such as spill clean-ups, or in situations when theatmospheric level is unknown.

Face and Eye ProtectionFor normal operations, chemical goggles shouldbe worn, along with hard hats. For situations inwhich the potential for exposure is greater, a faceshield is also recommended. When handlingDCP at elevated temperatures without sufficientventilation, the use of a NIOSH-approved, full-face, air-purifying respirator for organic vaporsis recommended.

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Protective ClothingWhen the potential for exposure exists, DowAgroSciences recommends protective clothingimpervious to DCP. The following personal pro-tective clothing is recommended: neoprene ornitrile gloves; neoprene boots; and Saranex,neoprene, or Kapler CPF3 full-body suit. UseDCP-impervious gloves at all times. Whenneeded, use gloves insulated for thermal protec-tion. Selection of specific personal protectiveequipment—such as face shield, boots, apron,or full-body suit—will depend on the operationsbeing undertaken.

Safety Showers and EyebathsSafety showers and eyebaths are essential in anyoperation involving DCP. They should be locatedin the immediate work area and readily acces-sible to personnel. Both should be tested rou-tinely and frequently to ensure proper operation.

First AidBecause of the toxicity of DCP, prompt actionafter exposure is necessary to minimize harm topersonnel. Emergency first-aid proceduresshould be covered thoroughly and reviewed fre-quently in worker training sessions. If you needhelp in planning or conducting such training,your Dow AgroSciences representative can as-sist you with more detailed information.

Note: First aid responders should pay atten-tion to self-protection and use the recommendedpersonal protective equipment (chemical resis-tant gloves, splash protection).

EyesUse an eyebath immediately, and irrigate eyescontinuously in flowing water for at least 30minutes. Prompt medical attention is essential.

SkinEnter the safety shower and immediately washthoroughly any size exposure with nonabrasivesoap and large quantities of water for 30 minutes,while removing contaminated clothing and foot-wear.

It is recommended that further amounts ofDCP be removed from the skin by repeatedlyspraying/swabbing with a polyethylene glycol orpolypropylene glycol mixture, alternating withrinsing with large quantities of water for 30 min-utes. Examples of decontamination mixturesinclude a 2:1 ratio of PEG300/ethanol (or indus-trial methylated spirits), available polypropy-lene/rapeseed oil proprietary mixtures, orpolyvinylpyrrolidone/detergent mixtures.

An option available in the U.S. is D-TAM®

Safe Solvent (Colorometric Labs, Des Plaines, IL;847-803-3737). Used undiluted, it is effective inremoving DCP from the skin. Apply gently toavoid abrading injured skin and promptly rinsewith water for 1 to 2 minutes. If water is unavail-able, wipe the material off with a paper towel.Follow up with repeated applications and rinse(or wipe) for 30 minutes.

A companion product, D-TAM Skin Cleanser,which also contains propylene glycol and emul-sifiers, has similar efficacy and is relatively in-terchangeable with D-TAM Safe Solvent.

Prompt medical attention is essential. Rapiddeath in humans has resulted from skin expo-sure to hot or molten DCP without immediatedecontamination.

IngestionDo not induce vomiting. Give large amounts ofwater or milk if available. Promptly transport in-dividual to a medical facility. Do not give any-thing by mouth to an unconscious person.

InhalationRemove to fresh air quickly if any ill effects oc-cur. Consult a physician.

Contaminated MaterialsDestroy and dispose of any items that cannot bedecontaminated, such as footwear, belts, watch-straps, etc.

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Shipping InformationContainersDCP can be supplied in bulk containers such asrail cars, tank trucks, or ISO tanks, or it can bepackaged in 55-gallon, galvanized-steel drums.Because DCP freezes at 108°F, it is very likelythat the shipment you receive from DowAgroSciences will require some degree of heat-ing before the container can be completely un-loaded into your storage system. Prior tounloading operations, review any written pro-cedures that have been established for handlingmolten DCP. Make sure all personnel unloadingthe containers are aware that the containers willneed to be safely vented to relieve excess pres-sure resulting from thawing of DCP. Either low-pressure steam or hot water can be used to meltDCP. Caution must be exercised when openingany container of molten DCP. To minimize therisk of exposure to DCP, the following minimumpersonal protective equipment is recommended:nitrile or neoprene gloves; neoprene boots;Saranex, neoprene, or Kapler CPF3 full-bodysuit; and face shield. In situations involvingpotential exposure to DCP vapors, a NIOSH-ap-proved, full-face, air-purifying respirator is rec-ommended.

Bulk VehiclesAll bulk vehicles used for the transportation ofDCP must be returned to the Dow AgroSciencesDCP production facility for decontaminationprior to being released for cleaning. Every effortwill be made to use dedicated equipment tominimize the number of vehicles in this service.This practice can affect the scheduling of prod-uct shipments.

Special RoutingDow AgroSciences will use two drivers whenmolten DCP must be shipped by tank truck.Restricted routing might be required for suchshipments. Adequate lead-time is necessary toensure that appropriate equipment, drivers, androutings are available.

Placarding and Labeling RequirementsRegulations require documentation, labeling,marking, placarding, and package/containerapproval for materials that meet certain criteria.

The shipping description must include theabove information and the emergency responsetelephone number. Any storage tank for DCPmust be properly identified and labeled. Othertank labels required by federal, state, or localregulations must also be installed.

Global Transportation [I.M.D.G.]—Dry orflake: TOXIC SOLIDS, CORROSIVE, ORGANIC,N.O.S. (2,4-DICHLOROPHENOL)/6.1/UN 2928/PG II/RQ (2,4-DICHLOROPHENOL) 100 LBS./MARINE POLLUTANT/EMS 6.1-04/MFAG 711/STCC=4921250

Land [North America]—Dry or flake: TOXICSOLIDS, CORROSIVE, ORGANIC, N.O.S. (2,4-DICHLOROPHENOL)/6.1/UN 2928/PG II/RQ(2,4-DICHLOROPHENOL) 100 LBS./MARINEPOLLUTANT.

Land [North America]—Molten or hot: TOXICLIQUID, CORROSIVE, ORGANIC, N.O.S. (2,4-DICHLOROPHENOL)/6.1/UN 2927/PG I/RQ(2,4-DICHLOROPHENOL) 100 LBS./MARINEPOLLUTANT/HOT.

LabelsTo display or print a copy of the dichlorophenolproduct label from the Dow AgroSciences website, visit www.dowagro.com, click on the “U.S.Label and MSDS System” link on the home page,and follow the on-screen instructions.

To obtain copies of the product label by fax,please call the Dow AgroSciences self-servicedocument center at 1-800-891-9157. If you arein California, call 1-888-847-6858 for the docu-ment center.

Copies of the label can also be ordered bytelephone from Dow AgroSciences CustomerService at 1-317-337-7850.

Transportation EmergenciesContact Dow AgroSciences Emergency Re-sponse at 1-800-992-5994 to speak with person-nel who will provide advice and arrange forprofessional help, as needed, to assist with anemergency.

Dow AgroSciences Emergency Response

1-800-992-5994

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SamplingThe proper approach for sampling solid DCPdepends on the working conditions and type ofcontainer or system from which the sample willbe obtained. Good judgement should be used todetermine the method for obtaining a represen-tative solid sample that minimizes the potentialfor exposure. Chemical goggles and imperviousgloves must be worn to obtain the sample.

Sampling hot or molten DCP should be doneusing a properly designed sampling system.Sampling devices should be placed in enclo-sures designed to isolate the product from per-sonnel and the environment. Wheneversamples are taken using such an enclosure,goggles and neoprene or nitrile glovesmust be worn. If an enclosure is not used,full protective clothing (imperviousgloves, boots, and suit) and a full-facerespirator must be worn. Direct samplingof hot or molten DCP should be avoided.

In any case, operating personnelshould review all sampling procedureswith supervision in advance to deter-mine the best sampling method andproper protective equipment re-quired for the task.

UnloadingBecause DCP is a solid at ambienttemperatures, tanks containingDCP will need to be thawed priorto unloading. Medium-pressuresteam is recommended for melt-ing DCP. The tank should beequipped with steam coils to aidin the thawing process. Whenunloading molten DCP, use anunloading checklist (see ex-ample at right). Review allwritten procedures estab-lished for your facility for un-loading DCP from a tank.

Wear appropriate protec-tive equipment, barricadethe immediate area, and re-strict access. Ensure thatsafety showers andeyebaths are locatednearby and are immedi-ately accessible and op-erational. Use extremecaution when connectingany unloading lines and steam lines to thetank. Monitor the transfer with another person

in attendance and, after transfer, blow out theunloading line with either nitrogen or dry air.

Unloading System DesignDCP is primarily shipped in top-unload, insu-lated tanks equipped with dry-disconnect fit-tings and external steam coils for melting thesolid DCP. The use of a pump to unload moltenDCP is recommended. A nitrogen pad can beused to help prime the transfer pump. A typicalunloading design is shown in Figure 1.

The storage tank should be vented back eitherto the bulk container or to a scrubber to avoidemissions of DCP. If the tank is vented to a scrub-

ber, the bulk container should bepadded with nitro-

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gen. Consideration should be made for purgingproduct from the unloading line to allow for aclean disconnect.

Safety showers and eyebaths should be in theunloading area and should be tested routinelyand frequently to ensure proper operation. Con-sideration should be made to contain leaks andavoid discharging DCP to the environment.

Warning!Molten DCP leaking through holes in piping, stor-age, or handling equipment will solidify whenexposed to normal ambient temperatures and canplug existing holes. Steam cleaning will melt theproduct. Precautions (use of all recommendedpersonal protection equipment) must be taken toavoid the potential for exposure from spraying orsplashing molten or hot product during clean-up,maintenance, repairs, etc.

For more information on DCP transportationor materials of construction issues, contact yourDow AgroSciences representative.

Spill Clean-UpUse the recommended personal protectiveequipment: neoprene or nitrile gloves; neopreneboots; face shield; and Saranex, neoprene, or

Kapler CPF3 full-body suit. Contain smallamounts of solid material and scoop into a steelor plastic container for disposal. Do not usewater to wash down spill area.

For molten DCP, wear full personal protectiveequipment (neoprene or nitrile gloves; neopreneboots, NIOSH-approved, full-face, air-purifyingrespirator; and Saranex, neoprene, or KaplerCPF3 full-body suit), contain and isolate thespill, and allow the material to solidify. Scoopsolid material into a steel or plastic container.For large spills, the use of self-contained breath-ing equipment should be considered.

Dispose of containers in accordance with allfederal, state, and local guidelines and regula-tions. Under no circumstances should DCP beallowed to enter public sewers (sanitary orstorm) or natural waters because of its toxicityto fish and aquatic organisms. See the MSDS fordetailed ecological information.

CERCLA/SARA Reportable QuantitiesA spill of 100 pounds or more of product is a re-portable quantity (RQ) and must be reported tofederal, state, and local emergency agencies.Verify with state and local agencies that this RQis applicable at your location.

FIGURE 1: Typical DCP unloading and storage system design: top unloading with a pump.

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StorageThe suggested material of construction for dryDCP storage and handling systems is carbonsteel. The use of copper is not recommendedbecause DCP at elevated temperatures is corro-sive to copper. If moisture is likely to be presentin the DCP, carbon steel is also unsuitable. Un-der these circumstances, only materials with agreater nickel content, such as Hastelloy C orMonel, should be used. Stainless steel should beavoided because of the potential for stress-corrosion cracking. Contact your DowAgroSciences representative for more informa-tion on materials of construction compatibilities.

Storage tanks should be equipped with a regu-lated nitrogen pad/depad system. The tankshould be vented to a scrubber system to avoidemissions of DCP. However, the scrubber mustbe properly isolated from the storage tank toavoid contamination of DCP with scrubber so-lution. Tank levels should be continuouslymonitored and have a redundant high-levelalarm. Secondary containment should be con-structed from or coated with an acid-resistantmaterial. Safety showers and eyebaths must belocated nearby and routinely and frequentlytested to ensure proper operation.

To clear piping and equipment for mainte-nance, all piping should be sloped to a low pointfor drainage and proper disposal in accordancewith all federal, state, and local guidelines andregulations. Double-block valve and bleed sys-tems should be used whenever possible to iso-late DCP from maintenance personnel. Tominimize the potential for contaminating theDCP system with water, no water lines shouldbe hard-piped into the system.

Warning!Molten DCP leaking through holes in piping, stor-age, or handling equipment will solidify whenexposed to normal ambient temperatures and canplug existing holes. Steam cleaning will melt theproduct. Precautions (use of all recommendedpersonal protection equipment) must be taken toavoid the potential for exposure from spraying orsplashing molten or hot product during clean-up,maintenance, repairs, etc.

Responsible Care® is a registered service mark of theAmerican Chemistry Council (ACC) in the UnitedStates.

Commitment toResponsible Care® andProduct StewardshipThis 2,4-Dichlorophenol Safe Handling Guidehas been prepared as part of Dow AgroSciences’product stewardship program and ResponsibleCare. Dow AgroSciences is dedicated to meet-ing the guiding principles of the global Respon-sible Care initiative. These principles emphasizecontinuous improvement in pollution preven-tion, employee health and safety, distribution,process safety, product stewardship, and com-munity awareness and emergency response.

This guide includes considerations for han-dling DCP and describes equipment suitable forstorage and handling of bulk quantities. Theguide details Dow AgroSciences’ interpretationof many codes and regulations relevant to thistype of product. If government requirements ap-plicable to your facility are more stringent, thoserequirements must be followed.

This guide is not intended as, and should notbe used as, a substitute for engineering or legaladvice. Applicable legislation and regulationsare constantly changing. Future regulatory andjudicial developments could necessitate changesto the procedures recommended in this guide.Each user or handler of 2,4-dichlorophenol isresponsible for compliance with all applicablefederal, state, and local laws, regulations, andcodes.

Dow AgroSciences urges you to review yourapplications and procedures regularly to ensurethat personnel handling DCP are thoroughlytrained and properly equipped. These individu-als should be aware of all potential hazards andshould know how to administer first aid. Formore information regarding this product, con-tact your Dow AgroSciences representative.

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Important Notes

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© 2000 by Dow AgroSciences LLC. All rights reserved. Y44-135-001 (9/00) ET

For more information call 1-317-337-7850.For emergency response information call 1-800-992-5994.

Responsible Care®

NOTICE: No freedom from any patent owned by Seller or others is to be inferred. Because use conditions and applicable laws may differ from

one location to another and may change with time, Customer is responsible for determining whether products and the information in this

document are appropriate for Customer’s use and for ensuring that Customer’s workplace and disposal practices are in compliance with ap-

plicable laws and other governmental enactments. Seller assumes no obligation or liability for the information in this document. NO WAR-

RANTIES ARE GIVEN: ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY

EXCLUDED.

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